BisfenolA en materiales y objetos destinados a estar en ...cresca-upc-events.cat/congres-parasitologia-2018/ponencies/enric-ri… · alteradores endocrinos 13/11/2018 Disruptores

BisfenolA en materiales y objetos destinados a estar en contacto con alimentos

Bisfenol A

13/11/2018 1

Hay dudas sobre la peligrosidad de este

producto. Unos dicen que es nocivo por

encima de 0.0005 %. Otros dicen que sólo

por encima de 0.0010 %


Conceptos fundamentales: • Es inevitable ingerir una parte del envase. Se estima que hay

unas 10 000 sustancias que pueden migrar desde los envases, incluyendo las llamadas añadidas de forma no intencionada (NIASs), por degradación del material o de sustancias que contiene)

• La mayoría de los requsitos sobre migración se refieren exclusivamente a los materiales poliméricos (plásticos)

• La cuestión no es si los componentes del envase van a migrar al alimento. Las preguntas que hay que hacerse son:

• ¿Cuáles son y cuáles son sus características toxicológicas?

• ¿En qué cantidades van a migrar?

13/11/2018 2


Evolución del número de casos de cáncer de testículos: Norte de Europa

13/11/2018 3

http://apps.who.int/iris/bitstream/handle/10665/78102/WHO_HSE_PHE_IHE_2013.1_eng.pdf;jsessionid=F91A21A966D62CF2292FD36FE61A1C95?sequence=1



Evolución del número de casos de cáncer de mama: Europa

13/11/2018 4




Incidencia de cáncer en niños y jóvenes en USA

13/11/2018 5




Evolución del número de casos de sobrepeso

13/11/2018 6




¿Qué es el Bisfenol A?

13/11/2018 7

TECHNOLOGY BPA is produced by the condensation of phenol and acetone in the presence of an acid catalyst (hydrogen chloride) and usually a promoter such as methyl mercaptan. Cationic ion exchange resins can replace the acid catalyst in newer plants. After the reaction and recovery of acid and phenol, the BPA is washed with water, neutralised with milk of lime and distilled under vacuum. Newer processes employ distillation and extractive crystallisation under pressure to purify the BPA. Two grades are produced: one for epoxy resin production and a higher purity grade for PC manufacture.

Bisphenol A (BPA) is a crystalline, prilled or flake material with a slightly phenolic odour.


Para qué

13/11/2018 8

A- production of polycarbonate (PC), which accounts for about 65% of consumption: Manufacture of modern optical media, such as DVDs and CDs, sports equipment, medical and dental devices, building and construction materials, automotive parts and domestic appliances, as well as food containers, such as reusable beverage bottles and some manufacturing equipment . B- epoxy resins, responsible for roughly 30% of consumption. C- Other uses include: • flame retardants (mainly tetrabromobisphenol A) • unsaturated polyester resins and polyacrylate, • thermal papers, (exposure of cashiers in frequent contact

with thermal paper in receipts) • polyetherimide and • polysulphone resins.

https://www.icis.com/chemicals/polycarbonate/

https://www.icis.com/chemicals/epoxy-resins/


¿Quién? (1)

13/11/2018 9


¿Quién? (2)

13/11/2018 10

Capacidad global: 8 mllones de Tm/año

Precios: Entre 900 y 2000 US$/Tm Mercado Mundial: Unos 12 billones de US$/año

Bisphenol A is among the highest volume of chemicals produced world-wide


Disruptores o alteradores endocrinos

13/11/2018 11

Esquema del Sistema endocrino: Glándulas endocrinas y algunos ejemplos de las hiormonas que producen

Las hormonas son substancias producidas por los tejidos endocrinos, como los ovarios, los testículos, las suprarrenales, la pituitaria o el páncreas , que se liberan en la sangre para actuar como mensajeros químicos, dirigiendo la comunicación y la coordinación entre otros tejidos del organismo. Las hormonas actúan sobre receptores de las células de destino. Estos receptores son específicos para cada hormona


13/11/2018 12

Un disruptor o alterador endocrino es una substáncia exógena o mezcla que altera funciones del sistema endocrino y en consecuencia causa trastornos de la salud en un organismo intacto, en su progenie o en sub-poblaciones del mismo Un disruptor endocrino potencial es una substáncia exógena o mezcla que tiene propiedades que cabe esperar que lleven a una disrupción endocrina en un organismo intacto, en su progenie o en sub-poblaciones


Disruptores endocrinos: Base estructural

13/11/2018 Migracions. nov. 2010 13

A comparison of the structures of the natural hormone estradiol (left) and one of the nonyl-phenols (right), an endocrine disruptor

http://en.wikipedia.org/wiki/Endocrine_disruptor

Pueden ser compuestos que se dan en la naturaleza o substancias artificiales. Imitan o interfieren con las funciones de las hormonas en el organismo. Pueden activar, desactivar o modificar las señales transmitidas por las hormonas y alterar así las funciones normales de tejidos y órganos. Se los ha relacionado con problemas del desarrollo, la reproducción , inmunológicos , neuronales, inmunológicos y otros. En animales salvajes y en el laboratorio. Algunas investigaciones sugieren que estas substancias afectan de formas similares a la salud humana con resultados como fertilidad reducida y aumento de las frecuencias de algunas enfermedades como obesidad, diabetes, endometriosis y algunos cánceres (por ejemplo, de mama y de próstata)

http://en.wikipedia.org/wiki/Estradiol

http://en.wikipedia.org/wiki/Nonylphenol


Mecanismos de acción de los disruptores endocrinos

13/11/2018 Disruptores endocrinos 14

Una vez absorbido por el organismo, el disruptor endocrino puede reducir o aumentar el nivel normal de hormonas (izquierda), imitar la producción de hormona natural (centro) o alterar la producción normal de hormonas (derecha)


Enfermedades relacionadas con la exposición a los alteradores endocrinos



Algunos alteradores endocrinos preocupantes


Alterador Principales vías de exposición Bisfenol A (BPA) Artículos en contacto con alimentos. Papel térmico Dioxinas Alimentos en general. Más en los de origen animal Atrazina Herbicida. Básicamente es un rsgo ocupacional. Ftalatos Envases y artículos en contacto con alimentos Perclorato Agua de consumo humano. Compite con el iodo Retardantes de llama

(Bifenilos polibromados) Tejidos, alfombras

Plomo Pigmentos en pinturas viejas de edificios Arsénico Agua de consumo humano Mercurio Alimentos. Sobre todo, pescado Compuestos perfluorados

Superfs. antiadherentes (Utensilios, tejidos, muebles)

Pesticidas organofosforados

Pesticidas en agricultura

Éteres de glicoles Productos de limpieza


Contaminantes químicos preocupantes

13/11/2018 17

The first list of HBM4EU priority substances includes: •Aniline family •Bisphenols •Cadmium and chromium VI •Chemical mixtures •Emerging substances •Flame retardants •PAHs •Per-/poly-fluorinated compounds •Phthalates and Hexamoll® DINCH

https://www.hbm4eu.eu/the-substances/


Peligros asociados con el Bisfenol A

13/11/2018 18

Bisphenol A could be associated with increased risk for: • Fetal development: miscarriages, decreased birth weight at

term, • Reproductive and sexual dysfunctions, • Breast and prostate cancer or at least significant breast

tissue remodelling. Studies have indicated that those effects were associated with gestational and neonatal exposure • Altered immune system activity, • Obesity and metabolic dysfunctions and diabetes in adults, • Cardiovascular disease in adults • Cognitive and behavioural development in young children.

https://www.hbm4eu.eu/wp-content/uploads/2017/03/scoping-documents-for-2018.pdf

Despite the wealth of studies, there are still controversies concerning the toxic effects of BPA. Those are related to some lack of reproducibility of the experimental studies possibly due to different designs.

https://www.hbm4eu.eu/wp-content/uploads/2017/03/scoping-documents-for-2018.pdf


Bisfenol A clasificado como disruptor endocríno

13/11/2018 19

Helsinki, 16 June 2017 - The Member State Committee unanimously agreed on the identification as substances of very high concern (SVHCs) of: •4,4'-isopropylidenediphenol (bisphenol A, BPA) (EC 201-245-8, CAS 80-05-7), proposed by France, due to its endocrine disrupting properties for human health; •Perfluorohexane-1-sulphonic acid and its salts (PFHxS), proposed by Sweden, due to their very persistent and very bioaccumulative (vPvB) properties. Bisphenol A is already listed in the Candidate List due to its toxic for reproduction properties.

https://echa.europa.eu/-/msc-unanimously-agrees-that-bisphenol-a-is-an-endocrine-disruptor

Regulation (EC) No 1907/2006 of the European Parliament and of the Council on the Registration, Evaluation, Authorisation and Restriction of Chemicals (REACH).






















http://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:02006R1907-20161011&from=EN

http://eur-lex.europa.eu/legal-content/EN/TXT/PDF/?uri=CELEX:02006R1907-20161011&from=EN


Vías de exposición

13/11/2018 20

There is evidence that contamination can occur through different routes, including food, water, air and skin (particularly in occupational exposure of cashiers).


Alternativas para substituir al bisfenol A (BPA):

13/11/2018 21

•Substituir directamente el BPA por otra substancia

•Substituir el plástico del que el BPA es un componente, por

otro plástico con propiedades funcionales parecidas (Por ej.

Copoliester);

•Substituir por otro tipo de material (Vidrio, metal, etc) o

por otro tipo de envase (Por. Ej tetrabrick);

•Substituir por un proceso diferente (Ej: Pagos sin contacto,

con el recibo pasado directamente al teléfono) https://www.anses.fr/en/content/potential-alternatives-bisphenol

https://www.anses.fr/en/content/potential-alternatives-bisphenol


Posibles alternativas para el Bisfenol A

13/11/2018 22

“These results for the first time demonstrate that BPS and BPF, like BPA, have potential to interfere with TH signaling pathway”

Yin-FengZhang et al. (2018) "Bisphenol A alternatives bisphenol S and bisphenol F interfere with thyroid hormone signaling pathway in vitro and in vivo", Environmental Pollution, Volume 237, June 2018, Pages 1072-1079


Algunos miembros de la familia de los bisfenoles

13/11/2018 23

Bisfenol A 4,4'-(propane-2,2-diyl)diphenol

Bisfenol S 4,4'-Sulfonyldiphenol

Pergafast 201 N-(p-Toluenesulfonyl) -N'-(3- p-toluenesulfonyloxyphenyl)urea

Urea urethane compound (UU)

D-8

Bisfenol F Bis(4- hydroxyphenyl) methane

Bisphenol AP, BPAP

4,4‟-(1- Phenylethylidene) bisphenol


Sustitutivos de Bisfenol A en papel térmico: Precios

13/11/2018 24


Enfoque de los fabricantes de papel térmico

13/11/2018 25

EU paper manufacturers have started to substitute BPA with BPS, The amount of BPS used as developer in thermal paper on the EU market almost doubled between 2016 and 2017. Reflecting the overall increase in the use of thermal paper in the EU in 2017, BPA use also increased in the same time period. (ECHA’s Risk Assessment Committee in its opinion on BPA indicated that BPS “is suspected to have many of the same adverse health effects as BPA”


Barnices: Características funcionales

13/11/2018 26

https://www.google.ch/url?sa=t&rct=j&q=&esrc=s&source=web&cd=7&cad=rja&uact=8&ved=0ahUKEwiltubd6KTNAhUFPhQKHcmID6sQFgg-MAY&url=http%3A%2F%2Fphx.corporate-ir.net%2FExternal.File%3Fitem%3DUGFyZW50SUQ9NTA5MzE5fENoaWxkSUQ9NTUxNzQ1fFR5cGU9MQ%3D%3D%26t%3D1&usg=AFQjCNGXJt0IfWHIqwECmla7SwKRCMmjuA

https://www.google.ch/url?sa=t&rct=j&q=&esrc=s&source=web&cd=7&cad=rja&uact=8&ved=0ahUKEwiltubd6KTNAhUFPhQKHcmID6sQFgg-MAY&url=http://phx.corporate-ir.net/External.File?item%3DUGFyZW50SUQ9NTA5MzE5fENoaWxkSUQ9NTUxNzQ1fFR5cGU9MQ%3D%3D%26t%3D1&usg=AFQjCNGXJt0IfWHIqwECmla7SwKRCMmjuA


Barnices: Formas de aplicación

13/11/2018 27

https://www.google.ch/url?sa=t&rct=j&q=&esrc=s&source=web&cd=7&cad=rja&uact=8&ved=0ahUKEwiltubd6KTNAhUFPhQKHcmID6sQFgg-MAY&url=http%3A%2F%2Fphx.corporate-ir.net%2FExternal.File%3Fitem%3DUGFyZW50SUQ9NTA5MzE5fENoaWxkSUQ9NTUxNzQ1fFR5cGU9MQ%3D%3D%26t%3D1&usg=AFQjCNGXJt0IfWHIqwECmla7SwKRCMmjuA

https://www.google.ch/url?sa=t&rct=j&q=&esrc=s&source=web&cd=7&cad=rja&uact=8&ved=0ahUKEwiltubd6KTNAhUFPhQKHcmID6sQFgg-MAY&url=http://phx.corporate-ir.net/External.File?item%3DUGFyZW50SUQ9NTA5MzE5fENoaWxkSUQ9NTUxNzQ1fFR5cGU9MQ%3D%3D%26t%3D1&usg=AFQjCNGXJt0IfWHIqwECmla7SwKRCMmjuA


Resinas epoxi: Obtención

13/11/2018 28


13/11/2018 29

Epoxy coatings In the 1950s, epoxy resins were introduced as coatings for aluminum and steel cans. Their stability, protective function, and technical properties made them the most commonly used coating material. Most epoxy coatings are synthesized from bisphenol A (BPA, CAS 80-05-7) and epichlorohydrin forming bisphenol A-diglycidyl ether epoxy resins. Many different blends of epoxy coatings were developed with epoxy-phenolic coatings being the most important subgroup. Other blended resins are e.g. epoxy amines, acrylates, and anhydrides. Oleoresins First can coatings were made of oleoresins, which are mixtures of oil and resin extracted from plants. Oleoresins are rather flexible and easily applied, but do not adhere well to metal surfaces, have a limited corrosion resistance, and need long curing times. Furthermore, they may change the organoleptic properties of food.

https://www.foodpackagingforum.org/food-packaging-health/can-coatings

https://www.foodpackagingforum.org/food-packaging-health/can-coatings


13/11/2018 30

Phenolic Phenolic resins are composed of phenols and aldehydes. They are highly corrosion resistant and protect cans from sulfide staining. Phenolics have low flexibility, do not adhere well to metal, and may change the odor and flavor of foods. They are applied as coatings for drums and pails, but unblended phenolic resins are not used in food and beverage cans. However, phenolics are common crosslinkers (e.g. in epoxide resins) and increase their resistance. Acrylic Acrylic resins are most commonly synthesized from ethylacrylate. They have a clean appearance and display corrosion and sulfide stain resistance, but they are brittle and may change the taste and odor of foods. Polyester Isophthalic acid (IPA) and terephthalic acid (TPA) are the main carboxylic acids used in polyester coatings. Polyester resins are easy to handle during the production process and adhere well to the metal surface, but they are usually not stable under acidic conditions and have a poor corrosion resistance. Alternatively, polyethylene terephthalate (PET) coatings are used to laminate beverage cans, but adhesives are needed to bind the PET onto the metal.


13/11/2018 31

Vinyl Vinyl coatings are synthesized from vinyl chloride and vinyl acetate. They are highly flexible and stable under acidic and alkaline conditions, but they do not adhere well on metal and do not withstand at high temperatures. Vinyl coatings need plasticizers and stabilizers and are often blended with other resins. Vinyl organosols are prepared from suspensions of resin in organic solvent. Organosols offer comparably higher chemical resistance, thermal stability, and adhesion properties than vinyl coatings. Phenolic Phenolic resins are composed of phenols and aldehydes. They are highly corrosion resistant and protect cans from sulfide staining. Phenolics have low flexibility, do not adhere well to metal, and may change the odor and flavor of foods. They are applied as coatings for drums and pails, but unblended phenolic resins are not used in food and beverage cans. However, phenolics are common crosslinkers (e.g. in epoxide resins) and increase their resistance. Polyolefins Coatings that are based on dispersions of polyolefins have recently entered the market. According to the manufacturer, the final polyolefin coating exhibits corrosion protection, adhesion, and flexibility without impacting the flavor of the food


Enfoque de los fabricantes de envases metálicos

13/11/2018 32

At least 90% of today’s food cans have replaced linings that previously contained the controversial chemical bisphenol-A (BPA), according to the Can Manufacturers Institute. “Food can linings now are typically made from acrylic and polyester. And all new materials are extensively tested and are cleared by regulatory agencies before being sold in the market.”

https://www.packagingdigest.com/food-packaging/most-food-cans-no-longer-use-bpa-in-their-linings-2018-02-20


Enfoque de los fabricantes de policarbonato: Copoliésteres

13/11/2018 33

2,2,4,4-Tetramethyl-1,3-cyclobutanediol (CBDO) Tritan (Eastman

Chemical Company)


Enfoque de los fabricantes de policarbonato: Marco legal en Europa

13/11/2018 34

Commission Directive 2002/72/EC of 6 August 2002 relating to plastic materials and articles intended to come into contact with foodstuffs [See amending acts]. SUMMARY Scope The Directive applies to plastic materials and articles intended to come into contact with foodstuffs. Such materials and articles, and parts thereof, may be composed either of plastic material only or of several layers of plastic material or of different types of materials. Approved substances Monomers and other starting substances which may be used in the manufacture of plastic materials and articles (Annex II); Additives which may be used in the manufacture of plastic materials and articles (Annex III). At the moment a new additive can always be included in the list after evaluation and authorisation by the European Food Safety Authority (EFSA).

https://eur-lex.europa.eu/legal-content/EN/AUTO/?uri=celex:32002L0072

https://eur-lex.europa.eu/legal-content/EN/TXT/?uri=LEGISSUM:l21301#amendingact

https://eur-lex.europa.eu/legal-content/EN/AUTO/?uri=uriserv:f80501


¿Qué hacer? ¿Sería efectivo prohibir el Bisfenol A?

13/11/2018 35

No parece fácil establecer una relación tan clara para el Bisfenol A porque sus efectos forman parte de los del resto de disruptores endocrinos.

BisfenolA en materiales y objetos destinados a estar en ...cresca-upc-events.cat/congres-parasitologia-2018/ponencies/enric-ri… · alteradores endocrinos 13/11/2018 Disruptores

Documents